JP6551394B2 - Polymer, composition for organic electroluminescence device, organic electroluminescence device, organic EL display device and organic EL lighting - Google Patents

Description

  The present invention relates to a polymer, and in particular, a polymer useful as a hole injection layer and a hole transport layer of an organic electroluminescence device, a composition for an organic electroluminescence device containing the polymer, and the organic electroluminescence device The present invention relates to an organic EL (Electro Luminescence) display device and organic EL illumination.

  Examples of the method for forming the organic layer in the organic electroluminescence device include a vacuum deposition method and a wet film formation method. Since vacuum deposition is easy to laminate, it has the advantages of improved charge injection from the anode and / or cathode and easy containment of the light emitting layer of excitons. On the other hand, the wet film formation method does not require a vacuum process, is easy to increase in area, and can be easily applied to a plurality of materials having various functions by using a coating liquid in which a plurality of materials having various functions are mixed. There are advantages such as the ability to form a layer containing the material of However, since the wet film forming method is difficult to stack, the driving stability is inferior to that of the element by the vacuum vapor deposition method, and the present state is that it has not reached a practical level except for a part.

  Then, in order to perform lamination by a wet film forming method, a charge transporting polymer having a crosslinkable group which is insolubilized after coating is desired, and its development has been carried out. Specifically, Patent Literatures 1 to 4 disclose benzocyclobutene having excellent durability as a crosslinkable group and a polymer having an arylamine structure having excellent transportability as a charge transporting site.

International Publication No. 2009/123269 International Publication No. 2011/078387 International Publication No. 2011/093428 International Publication No. 2013/191137

  According to the study by the present inventors, in order to insolubilize the polymer containing benzocyclobutene described in Patent Documents 1 to 4, large energy is required, and high temperature and long time baking is required. It turns out that problems arise. Specifically, it has been found that in a substrate, a partition, an insulating film, and a display device, the heat resistance of a member such as a TFT has to be improved, and since a long time is required for baking, elements can be manufactured only in small amounts. The

  Therefore, it is an object of the present invention to provide a polymer having a high hole injecting and transporting ability and a high durability, which can be insolubilized at a low temperature and a short time, and a composition for an organic electroluminescent device containing the polymer. Do. Another object of the present invention is to provide an organic electroluminescent device which can be easily manufactured, which has high luminance and long driving life.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by using a polymer having a specific crosslinkable group, and have completed the present invention.

That is, the present invention has the following structures [1] to [12].
[1] A polymer having a crosslinkable group represented by the following formula (1).

(The 1,2-dihydrocyclobuta [a] naphthalene ring in formula (1) may have a substituent.)
[2] The polymer according to [1], including a repeating unit represented by the following formula (2).

(In Formula (2), p represents an integer of 0 or more and 3 or less, and Ar ¹ and Ar ² are each independently a direct bond, an aromatic hydrocarbon group which may have a substituent, or a substituent. Represents an aromatic heterocyclic group which may have a group, and Ar ^{3 to} Ar ⁵ may each independently have an aromatic hydrocarbon group or a substituent which may have a substituent. It represents a good aromatic heterocyclic group, provided that neither Ar ¹ nor Ar ² is a direct bond.
[3] The polymer according to [1], including a repeating unit represented by the following formula (3).

(In Formula (3), q represents an integer of 0 or more and 3 or less, and R ¹ may have a C 1-24 alkyl group which may have a substituent, or a substituent. Represents an aromatic hydrocarbon group which may have an aromatic hydrocarbon group or a substituent, and Ar ⁶ and Ar ⁷ each independently represents a direct bond, an aromatic hydrocarbon which may have a substituent Represents an aromatic heterocyclic group which may have a group or a substituent, and Ar ^{8 to} Ar ¹² each independently have an aromatic hydrocarbon group or a substituent which may have a substituent. Or an aromatic heterocyclic group which may be substituted, provided that neither Ar ⁶ nor Ar ⁷ is a direct bond.
[4] The polymer according to [1], including a repeating unit represented by the following formula (4).

(In the formula (4), r represents an integer of 0 or more and 3 or less, and Ar ¹³ , Ar ¹⁴ , Ar ¹⁶ and Ar ¹⁷ are each independently an aromatic hydrocarbon group which may have a substituent. Or, it represents an aromatic heterocyclic group which may have a substituent, and Ar ¹⁵ may have a direct bond, an aromatic hydrocarbon group which may have a substituent, or a substituent. Represents an aromatic heterocyclic group)
[5] The polymer according to any one of [1] to [4], wherein the weight average molecular weight (Mw) is 20,000 or more and the dispersity (Mw / Mn) is 2.5 or less.

[6] A composition for an organic electroluminescent device, comprising the polymer according to any one of the above [1] to [5].
[7] An organic electroluminescent device having an anode, a cathode, and an organic layer between the anode and the cathode on a substrate, wherein the organic layer is the composition for an organic electroluminescent device according to the above [6] An organic electroluminescent element including a layer formed by a wet film-forming method using an object.
[8] The organic electroluminescence device according to [7], wherein the layer formed by the wet film formation method is at least one of a hole injection layer and a hole transport layer.
[9] A hole injection layer, a hole transport layer, and a light emitting layer are included between the anode and the cathode, and the hole injection layer, the hole transport layer, and the light emitting layer are all formed by a wet film forming method. The organic electroluminescent device according to the above [7] or [8].
[10] An organic EL display device having the organic electroluminescent element as described in any one of [7] to [9].
[11] Organic EL lighting having the organic electroluminescent element as described in any one of [7] to [9].
[12] A compound represented by the following formula (5).

(In formula (5), X represents a halogen atom.)

  The layer obtained by wet film formation using the composition for an organic electroluminescent element containing the polymer of the present invention is flat without causing cracks and the like. According to the organic electroluminescent element of the present invention, the luminance is high and the driving life is long.

FIG. 1 is a schematic cross-sectional view showing a structural example of an organic electroluminescent element of the present invention.

Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention does not exceed the gist thereof. Not specified in the content of.
Moreover, in the present specification, percentages and parts represented by "mass" are synonymous with percentages and parts represented by "weight".

<Polymer>
The polymer of the present invention has a crosslinkable group represented by the following formula (1).

(The 1,2-dihydrocyclobuta [a] naphthalene ring in formula (1) may have a substituent.)

  As the substituent which may be possessed by the 1,2-dihydrocyclobuta [a] naphthalene ring in the formula (1), those which hardly interfere with the crosslinking reaction are preferable. Examples thereof include 12 alkyl groups and alkoxy groups having 1 to 12 carbon atoms.

  The crosslinkable group represented by the formula (1) is opened by heat as shown in the following reaction formula (6). The activation energy of the ring-opening reaction of the following reaction formula (6) is smaller than the activation energy of the ring-opening reaction of benzocyclobutene which has conventionally been used as a crosslinkable group.

  After ring opening, an addition reaction proceeds as in the following reaction formula (7).

In a series of cross-linking reactions, the ring-opening reaction usually requires a larger activation energy than the addition reaction. Therefore, in the polymer containing the formula (1) having 1,2-dihydrocyclobuta [a] naphthalene as a crosslinkable group and having a low activation energy for the ring-opening reaction, insolubilization at a low temperature in a short time becomes possible. is there.
That is, the insolubilization rate at low temperature of the polymer having a crosslinkable group represented by the above formula (1) depends on the crosslinkable group represented by the above formula (1). The polymer of (1) can achieve insolubilization at low temperature in a short time.

  The partial structure suitable for charge transport includes a triarylamine structure; a fluorene ring, anthracene ring, pyrene ring, carbazole ring, dibenzofuran ring, dibenzothiophene ring, phenoxazine ring, phenanthroline ring, and other aromatic ring structures An aromatic heterocyclic structure such as a pyridine ring, a pyrazine ring, a triazine ring, a quinoline ring, a thiophene ring, a silole ring, an imidazole ring, a pyrazole ring, an oxadiazole ring, a benzothiadiazole ring; a metal complex structure, etc. The triarylamine structure is preferred in terms of excellent hole transportability.

  The polymer of the present invention preferably contains a repeating unit represented by the following formula (2) from the viewpoint of improving charge transportability.

(In the formula (2), p represents an integer of 0 or more and 3 or less,
Ar ¹ and Ar ² each independently represent a direct bond, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent,
Ar ^{3 to} Ar ⁵ each independently represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent,
However, neither Ar ¹ nor Ar ² is a direct bond. )

  The crosslinkable group in the formula (2) is present from the triarylamine structure via at least one single bond, and the crosslinkable group is unlikely to hinder charge transport, so that the charge transportability is further improved.

  The polymer of the present invention preferably contains a repeating unit represented by the following formula (3) in that the charge transportability is improved and the polymer is insolubilized under milder conditions.

(In the formula (3), q represents an integer of 0 or more and 3 or less,
R ¹ represents an alkyl group having 1 to 24 optionally having a substituent, an aromatic hydrocarbon group optionally having a substituent, or an aromatic heterocyclic group optionally having a substituent. Represent,
Ar ⁶ and Ar ⁷ each independently represent a direct bond, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent,
Ar ^{8 to} Ar ¹² each independently represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent,
However, neither Ar ⁶ nor Ar ⁷ is a direct bond. )

Since the carbon atom at the center of the sp3 hybrid orbital in the formula (3) does not participate in the π conjugated system, the crosslinkable group which is a side chain bonded to the carbon atom at the center of the sp3 hybrid orbital interferes with charge transport. It is difficult to improve the charge transportability.
The atom at the center of the sp3 hybrid orbital is more susceptible to rotation of bonding than the atom at the center of the sp2 hybrid orbital, so the crosslinkable groups in the polymer react efficiently, so the number of crosslinkable groups is Even if the amount is small or the conditions for the crosslinking reaction are mild, it can be hardly soluble in the organic solvent.

  The polymer of the present invention preferably contains a repeating unit represented by the following formula (4) from the viewpoint of improving charge transportability.

(In the formula (4), r represents an integer of 0 or more and 3 or less,
Ar ¹³ , Ar ¹⁴ , Ar ¹⁶ and Ar ¹⁷ each independently represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent,
Ar ¹⁵ represents a direct bond, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. )

  The crosslinkable group in the formula (4) is present from the arylene group of the main chain via at least one single bond, and the crosslinkable group is less likely to hinder charge transport, and charge transportability is further improved.

[Ar ^{1 to} Ar ¹⁷ ]
In formulas (2) to (4), Ar ¹ , Ar ² , Ar ⁶ , Ar ⁷ and Ar ¹⁵ are each a direct bond, a divalent aromatic hydrocarbon group which may have a substituent, or a substituent. Represents a divalent aromatic heterocyclic group which may have a group. A plurality of the aromatic hydrocarbon groups and aromatic heterocyclic groups may be bonded.

Ar ³ , Ar ⁴ , Ar ⁸ , Ar ⁹ , Ar ¹⁰ and Ar ¹⁴ are each a divalent aromatic hydrocarbon group which may have a substituent, or a divalent which may have a substituent. And an aromatic heterocyclic group of A plurality of the aromatic hydrocarbon groups and aromatic heterocyclic groups may be bonded.

Ar ¹³ represents a trivalent aromatic hydrocarbon group which may have a substituent or a trivalent aromatic heterocyclic group which may have a substituent. A plurality of the aromatic hydrocarbon groups and aromatic heterocyclic groups may be bonded.

Ar ⁵ , Ar ¹¹ , Ar ¹² , Ar ¹⁶ and Ar ¹⁷ are each a monovalent aromatic hydrocarbon group which may have a substituent or a monovalent aromatic which may have a substituent. Represents a heterocyclic group. A plurality of the aromatic hydrocarbon groups and aromatic heterocyclic groups may be bonded.

  The aromatic hydrocarbon ring group preferably has 6 to 30 carbon atoms. For example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene. Examples thereof include 6-membered mono- or 2-5-membered monovalent or divalent groups such as a ring, a fluoranthene ring and a fluorene ring.

  The aromatic heterocyclic group preferably has 3 to 30 carbon atoms, for example, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring. , Pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, furofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine Ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring, etc. 5- or 6-membered ring Monovalent or divalent radical of a monocyclic or 2-4 fused ring may be mentioned.

  An aromatic hydrocarbon ring group is preferable from the viewpoint of excellent charge transportability and durability, and among them, a divalent group of a benzene ring and a fluorene ring, that is, a phenylene group and a fluorenylene group are more preferable. A phenylene group, a 1,4-phenylene group, and a 2,7-fluorenyl group are even more preferable.

  When the aromatic hydrocarbon group and the aromatic heterocyclic group are a plurality of bonded groups, 2 to 6 of these groups are linked from the viewpoint of excellent charge transportability and durability. preferable. The aromatic hydrocarbon group and aromatic heterocyclic group to be linked may be one kind or plural kinds.

Further, when a plurality of aromatic hydrocarbon groups and aromatic heterocyclic groups are bonded, they may be bonded through a linking group. In this case, examples of the linking group include a group selected from the group consisting of —CR ² R ³ —, —O—, —CO—, —NR ⁴ —, and —S—, and a group in which 2 to 10 thereof are linked. preferable. When two or more are connected, the linking group may be one kind or plural kinds. Here, R ^{2 to} R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 24 carbon atoms which may have a substituent, an aromatic hydrocarbon group which may have a substituent, Represents an aromatic heterocyclic group which may have a substituent. As the linking group, —CR ² R ³ — and 2 to 6 linked —CR ² R ³ — are particularly preferable, and —CR ² R ³ — is more preferable.

  The substituent that the aromatic hydrocarbon ring group or the aromatic heterocyclic group may have is not particularly limited as long as it does not significantly reduce the properties of the present polymer. For example, from the following substituent group Z The group to be selected is mentioned, and an alkyl group, an alkoxy group, an aromatic hydrocarbon ring group and an aromatic heterocyclic group are preferable, and an alkyl group is more preferable.

[Substituent group Z]
For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-hexyl group, cyclohexyl group, dodecyl group, etc. A linear, branched or cyclic alkyl group having a carbon number of usually 1 or more, usually 24 or less, preferably 12 or less;
For example, an alkenyl group having a carbon number of usually 2 or more, usually 24 or less, preferably 12 or less, such as a vinyl group;
For example, alkynyl groups having a carbon number of usually 2 or more, usually 24 or less, preferably 12 or less, such as ethynyl group;
For example, an alkoxy group having a carbon number of usually 1 or more, and usually 24 or less, preferably 12 or less, such as methoxy group and ethoxy group;
For example, an aryloxy group having usually 4 or more, preferably 5 or more, usually 36 or less, preferably 24, such as a phenoxy group, a naphthoxy group, or a pyridyloxy group;
For example, an alkoxycarbonyl group having 2 or more carbon atoms, usually 24 or less, preferably 12 or less, such as a methoxycarbonyl group or an ethoxycarbonyl group;
For example, a dialkylamino group having 2 or more carbon atoms and usually 24 or less, preferably 12 or less, such as a dimethylamino group or a diethylamino group;
For example, a diarylamino group having a carbon number of usually 10 or more, preferably 12 or more, usually 36 or less, preferably 24 or less, such as a diphenylamino group, a ditolylamino group, or an N-carbazolyl group;
For example, an arylalkylamino group having a carbon number of usually 7 or more, and generally 36 or less, preferably 24 or less, such as phenylmethylamino group;
For example, an acyl group having a carbon number of usually 2 or more, and usually 24 or less, preferably 12 or less, such as acetyl group and benzoyl group;
For example, a halogen atom such as a fluorine atom or a chlorine atom;
For example, a haloalkyl group having a carbon number of usually 1 or more, usually 12 or less, preferably 6 or less, such as trifluoromethyl group;
For example, an alkylthio group having a carbon number of usually 1 or more, and usually 24 or less, preferably 12 or less, such as methylthio group and ethylthio group;
For example, an arylthio group having a carbon number of usually 4 or more, preferably 5 or more, usually 36 or less, preferably 24 or less, such as a phenylthio group, a naphthylthio group, or a pyridylthio group;
For example, a silyl group having a carbon number of usually 2 or more, preferably 3 or more, and usually 36 or less, preferably 24 or less, such as trimethylsilyl group and triphenylsilyl group;
For example, siloxy groups having a carbon number of usually 2 or more, preferably 3 or more, and usually 36 or less, preferably 24 or less, such as trimethylsiloxy group and triphenylsiloxy group;
A cyano group;
For example, an aromatic hydrocarbon ring group having a carbon number of usually 6 or more, and usually 36 or less, preferably 24 or less, such as phenyl group and naphthyl group;
For example, an aromatic heterocyclic group having a carbon number of usually 3 or more, preferably 4 or more, and usually 36 or less, preferably 24 or less, such as thienyl group and pyridyl group.

  Among these substituents, from the viewpoint of solubility, alkyl groups having 1 to 12 carbon atoms and alkoxy groups having 1 to 12 carbon atoms are preferable.

  In addition, each of the above-mentioned substituents may further have a substituent, and as an example, it is selected from the groups exemplified in the section of [Substituent Group Z].

[R ¹ ]
In the formula (3), R ¹ has a hydrogen atom, an optionally substituted alkyl group having 1 to 24 alkyl groups, an optionally substituted aromatic hydrocarbon group or a substituent group. Represents an aromatic heterocyclic group which may be substituted. The alkyl group is a linear, branched or cyclic alkyl group having a carbon number of usually 1 or more and usually 24 or less, preferably 12 or less. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-hexyl group, cyclohexyl group, dodecyl Group. When R ¹ is an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent, specific examples and preferred examples are Ar ⁵ , Ar ¹¹ , Ar ¹² , Ar ¹⁶ and Ar ¹⁷ are the same.

  In formulas (2) to (4), p, q, and r are each an integer of 0 or more and 3 or less. Each of p, q and r is preferably 2 or less.

[Molecular weight of polymer]
The weight average molecular weight (Mw) of the polymer of the present invention is usually 3,000,000 or less, preferably 1,000,000 or less, more preferably 500,000 or less, further preferably 200,000 or less, Usually, it is 2,500 or more, preferably 5,000 or more, more preferably 10,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more.

  When the weight average molecular weight of the polymer exceeds the above upper limit value, the solubility in a solvent is lowered, so that the film forming property may be impaired. When the weight average molecular weight of the polymer is less than the above lower limit value, the glass transition temperature, the melting point and the vaporization temperature of the polymer may be lowered, so the heat resistance may be lowered.

  Also, the number average molecular weight (Mn) in the polymer of the present invention is usually 2,500,000 or less, preferably 750,000 or less, more preferably 400,000 or less, and usually 2,000 or more, preferably It is 4,000 or more, more preferably 8,000 or more, and still more preferably 20,000 or more.

  Furthermore, the degree of dispersion (Mw / Mn) in the polymer of the present invention is preferably 3.5 or less, more preferably 2.5 or less, and particularly preferably 2.0 or less. The lower limit value of the degree of dispersion is 1. When the degree of dispersion of the polymer is not more than the above upper limit, solubility in a solvent and charge transporting ability are good.

  In the present invention, the polymer of the present invention preferably has a weight average molecular weight of 20,000 or more and a dispersion degree of 2.5 or less. The polymer in which the weight average molecular weight and the degree of dispersion satisfy the above range is preferable because it has few components of low molecular weight and it is easily made insoluble.

  Usually, the weight average molecular weight and dispersion degree of a polymer are determined by SEC (size exclusion chromatography) measurement. In SEC measurement, the elution time is shorter for higher molecular weight components and the elution time is longer for lower molecular weight components, but using the calibration curve calculated from the elution time of polystyrene (standard sample) with a known molecular weight, the elution time of the sample is changed to the molecular weight. By conversion, the weight average molecular weight and the degree of dispersion are calculated.

[Number of crosslinkable groups]
The crosslinkable group possessed by the polymer of the present invention is preferably larger in that it is sufficiently insolubilized by crosslinking, and other layers can be easily formed thereon by a wet film forming method. On the other hand, it is preferable that the number of crosslinkable groups is small from the viewpoint that cracks are not easily generated in the formed layer, unreacted crosslinkable groups hardly remain, and the organic electroluminescent element tends to have a long life.
In the polymer of the present invention, the crosslinkable group present in one polymer chain is usually 1 or more on average, preferably 2 or more on average, and usually 200 or less, preferably 100 or less.

  The number of crosslinkable groups possessed by the polymer of the present invention can be represented by the number per 1000 molecular weight of the polymer. The number of crosslinkable groups per 1000 molecular weight of the polymer can be calculated from the molar ratio of the charged monomers at the time of synthesis and the structural formula, excluding the terminal group from the polymer. For example, in the case of the polymer 1 synthesized in the examples described later, in the polymer 1, the average molecular weight of repeating units excluding end groups is 840.71 and the crosslinkable group is per repeating unit The average is 0.111. When this is calculated by simple proportion, the number of crosslinkable groups per 1000 molecular weight is calculated to be 0.13.

  When the number of crosslinkable groups contained in the polymer of the present invention is represented by the number per 1000 molecular weight of the polymer, the number is usually 3.0 or less, preferably 2.0 or less, more preferably 1 per 1000 molecular weight. It is not more than 0, usually not less than 0.01, preferably not less than 0.05.

  When the number of crosslinkable groups is in the above range, cracks and the like are less likely to occur, and a flat film is easily obtained. In addition, since the crosslink density is appropriate, the amount of unreacted crosslinkable groups remaining in the layer after the crosslink reaction is small, which hardly affects the life of the obtained device.

  Furthermore, since the low solubility with respect to the organic solvent after the crosslinking reaction is sufficient, it is easy to form the multilayer lamination structure in the wet film forming method.

[Concrete example]
Hereinafter, specific examples of the polymer of the present invention will be listed.
These polymers may be any of random copolymers, alternating copolymers, block copolymers, graft copolymers, and the like, and are not limited to the sequence of monomers.

  The polymer of the present invention is preferably used for an organic electroluminescence device having an insulating film made of a resin. The reason is that the insulating film made of resin has relatively low heat resistance, so that the lower the temperature at the time of manufacturing the organic electroluminescent element, the more the decomposition of the insulating film made of resin and the release of gas can be suppressed. Here, the insulating film made of a resin is an anode on the substrate, an auxiliary electrode, a planarization film that covers some unevenness, or a film that partitions an electrode, and includes a partition that partitions a pixel and a light emitting region. Some unevenness is, for example, a particle-containing layer for scattering light, a TFT provided in a display device, or the like. As the insulating film resin, polyimide resin, polyolefin resin, and acrylic resin are preferable. Moreover, it is more preferable to use the polymer of this invention for the organic electroluminescent element for organic electroluminescent display devices in which the insulating film which consists of resin is used.

<Synthesis method>
The monomer having a crosslinkable group represented by the formula (1) in the polymer of the present invention can be synthesized via a halide represented by the formula (5).

(In formula (5), X represents a halogen atom.)

  In the formula (5), examples of the halogen atom include I, Br, Cl, F and the like, and I, Br, and Cl are preferable from the viewpoint that the next reaction easily proceeds.

  The halide represented by the formula (5) is a carboxylic acid such as N-bromosuccinimide and N-bromophthalimide as shown in the following reaction formula (8): 1,2-dihydrocyclobuta [a] naphthalene By acting N-halide of imide, 4-position is selectively halogenated and can be obtained efficiently.

(In the above reaction formula, X represents a halogen atom.)

  As a conventional method for obtaining a halide of benzocyclobutene which is a crosslinkable group, bromine has been used as shown in the following reaction formula (9) (European Patent No. 346959, J. Am. Chem. Soc. 2011, 133, 49, 19864). However, when bromine is allowed to act on 1,2-dihydrocyclobuta [a] naphthalene, other than the 4-position is brominated, so that the target product cannot be obtained efficiently.

  A known coupling method can be applied as a method of deriving a monomer from a halide represented by Formula (5). For example, it is synthesized by Suzuki reaction as in the following formula.

(In the above reaction formula, X represents a halogen atom, G represents a group that reacts during polymerization, BR ₂ represents a boronic acid group or a boronic ester group, Ar ¹ , Ar ^4, and Ar ^13. Each independently represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent.

(In the above reaction formula, X represents a halogen atom, G represents a group that reacts during polymerization, BR ₂ represents a boronic acid group or a boronic ester group, and R ¹ represents a hydrogen atom, an alkyl group. Represents a group, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent, Ar ⁶ , Ar ⁸ and Ar ¹⁰ are each independently And an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent.

  The method for producing the polymer of the present invention is not particularly limited, and is arbitrary as long as the polymer of the present invention can be obtained. For example, it can be produced by a polymerization method by Suzuki reaction, a polymerization method by Grignard reaction, a polymerization method by Yamamoto reaction, a polymerization method by Ullmann reaction, a polymerization method by Buchwald-Hartwig reaction, or the like.

In the case of the polymerization method by the Ullmann reaction and the polymerization method by the Buchwald-Hartwig reaction, for example, a primary aminoaryl represented by the formula (1a) (Ar ⁴ is as defined above) and a formula (2a) Dihalogenated aryl (X represents a halogen atom such as I, Br, Cl, F, etc., Ar ² , Ar ³ and Ar ⁵ are as defined above, and p is an integer of 0 or more and 3 or less). The polymer of the present invention is synthesized by

And dihalogenated aryl represented by the formula (3a) (X represents a halogen atom such as I, Br, Cl, F, etc., and R ¹ , Ar ⁶ , Ar ⁸ and Ar ¹⁰ are as defined above). By reacting primary or secondary aminoaryl represented by formula (4a) (Ar ⁹ , Ar ¹¹ , Ar ¹² are as defined above, q is an integer of 0 or more and 3 or less). , The polymer of the present invention is synthesized.

  In the above polymerization method, the reaction for forming an N-aryl bond is usually carried out in the presence of a base such as potassium carbonate, tert-butoxy sodium, triethylamine or the like. Moreover, it can also carry out in presence of transition metal catalysts, such as copper and a palladium complex, for example.

In the case of the polymerization method by the Suzuki reaction, for example, a boron derivative represented by the formula (1b) (BR ₂ represents a boronic acid group or a boronic ester group, and Ar ¹ , Ar ^4, and Ar ¹³ have the same meanings as described above. And dihalogenated aryl represented by the formula (2b) (X represents a halogen atom such as I, Br, Cl, F, etc., Ar ² , Ar ³ and Ar ⁵ are as defined above, and p is 0 The polymer of this invention is synthesize | combined by making it react above.

And a boron derivative represented by the formula (3b) (BR ₂ represents a boronic acid group or a boronic ester group, and R ¹ , Ar ⁶ , Ar ⁸ and Ar ¹⁰ are as defined above) and a formula ((b) 4b) (X represents a halogen atom such as I, Br, Cl, F, etc., Ar ⁹ , Ar ¹⁰ and Ar ¹² are as defined above, and p is an integer of 0 or more and 3 or less. The polymer of the present invention is synthesized by reacting

  In the above-mentioned polymerization method, the reaction step of the boron derivative and the dihalide is usually carried out in the presence of a base such as potassium carbonate, tert-butoxy sodium or triethylamine. Moreover, it can also carry out in presence of transition metal catalysts, such as copper and a palladium complex, as needed. Further, the reaction step with the boron derivative can be performed in the presence of a base such as potassium carbonate, potassium phosphate, tert-butoxy sodium, triethylamine, and a transition metal catalyst such as a palladium complex.

  In addition to the above-described polymerization method, the charge-transporting polymer of the present invention may be the polymerization method described in JP-A-2001-223084, the polymerization method described in JP-A-2003-213002, Japan The polymerization method described in Japanese Patent Application Laid-Open No. 2004-2740, radical polymerization of a compound having an unsaturated double bond, and sequential polymerization by a reaction forming an ester bond or an amide bond can be used.

  Other known coupling reactions can be used. As a known coupling technique, specifically, “Palladium in Heterocyclic Chemistry: A guide for the Synthetic Chemist” (2nd edition, 2002, Jie Jack Li and Gordon Metals, Gr. Organic synthesis to open up its various reaction forms and latest results "(1997, Junjiro, Kagaku Dojinsha)," Under Bolhard Shore Modern Organic Chemistry "(2004, KPC Vollhardt, Kagaku Dojinsha) A ring-to-ring coupling reaction (coupling reaction) such as a coupling reaction of an aryl halide with an aryl borate described or cited in the like can be used.

  As described above, the partial structure represented by the formula (1) is previously bonded to a monomer that is a raw material of the polymer of the present invention, and polymerized to polymerize the polymer of the present invention. After synthesis of the moiety corresponding to the main chain of the polymer of the present invention, the partial structure represented by the formula (1) may be bonded to the desired moiety.

  Methods for purifying compounds include “Separation and Purification Technology Handbook” (1993, edited by The Chemical Society of Japan), “Advanced separation of trace components and difficult-to-purify substances by chemical conversion methods” (1988, IP Corporation). The known techniques can be used, including the methods described in the “Separation and Purification” section of “Citation,” or “Experimental Chemistry Course (4th edition) 1” (1990, edited by The Chemical Society of Japan). It is. Specifically, extraction (including suspension washing, boiling washing, ultrasonic washing, acid-base washing), adsorption, storage, melting, crystallization (including recrystallization from solvent, reprecipitation), distillation (atmospheric pressure) Distillation, vacuum distillation), evaporation, sublimation (atmospheric pressure sublimation, vacuum sublimation), ion exchange, dialysis, filtration, ultrafiltration, reverse osmosis, pressure osmosis, zone lysis, electrophoresis, centrifugation, flotation separation, sedimentation separation, Magnetic separation, various chromatography (shape classification: column, paper, thin layer, capillary, mobile phase classification: gas, liquid, micelle, supercritical fluid. Separation mechanism: adsorption, distribution, ion exchange, molecular sieve, chelate, gel filtration , Exclusion, affinity) and the like.

As a method for confirmation of the product and analysis of purity, gas chromatography (GC), high performance liquid chromatography (HPLC), high speed amino acid analyzer (organic compound), capillary electrophoresis measurement (CE), size exclusion chromatography (SEC) , Gel permeation chromatography (GPC), cross-fractionation chromatography (CFC), mass spectrometry (MS, LC / MS, GC / MS, MS / MS), nuclear magnetic resonance device (NMR ( ¹ H NMR, ¹³ C NMR)), Fourier Transform Infrared Spectrometer (FT-IR), UV Visible Near Infrared Spectrometer (UV. VIS, NIR), Electron Spin Resonance Device (ESR), Transmission Electron Microscope (TEM-EDX) Electron Micrograph (EPMA) ), Metal element analysis (ion chromatography, inductively coupled plasma-emission spectroscopy (ICP-AES) atomic absorption) Analysis (AAS), fluorescent X-ray analyzer (XRF)), nonmetal element analysis, trace analysis (ICP-MS, GF-AAS, optionally a GD-MS), etc., are applicable.

[Composition for Organic Electroluminescent Device]
The composition for organic electroluminescent elements of the present invention contains the polymer of the present invention. In addition, the composition for organic electroluminescent elements of the present invention may contain one type of the polymer of the present invention, or may contain two or more types in any combination and in any ratio. Good.

{Polymer content}
The content of the polymer of the present invention in the composition for an organic electroluminescent element of the present invention is usually 0.01 to 70% by mass, preferably 0.1 to 60% by mass, more preferably 0.5 to 50%. %.
It is preferable for the thickness to be within the above range, since defects in the formed organic layer are less likely to occur and film thickness unevenness is less likely to occur.

  The composition for organic electroluminescent element in the present invention can contain a solvent and the like in addition to the polymer according to the present invention.

{solvent}
The composition for organic electroluminescent device of the present invention usually contains a solvent. The solvent is preferably one that dissolves the polymer of the present invention. Specifically, a solvent that dissolves the polymer of the present invention at room temperature is usually 0.05% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more.

  Specific examples of the solvent include aromatic solvents such as toluene, xylene, mesitylene, cyclohexylbenzene; halogen-containing solvents such as 1,2-dichloroethane, chlorobenzene, o-dichlorobenzene; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene Aliphatic ethers such as glycol-1-monomethyl ether acetate (PGMEA), 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, Ether solvents such as aromatic ethers such as 2,3-dimethylanisole and 2,4-dimethylanisole; aliphatic esters such as ethyl acetate, n-butyl acetate, ethyl lactate and n-butyl lactate; phenyl acetate, pro Organic solvents such as ester solvents such as aromatic esters such as phenyl onate, methyl benzoate, ethyl benzoate, isopropyl benzoate, propyl benzoate and n-butyl benzoate; and other hole injection layer formation described below And organic solvents used for the composition for forming a hole and the composition for forming a hole transport layer.

In addition, a solvent may use one type and may use two or more types together by arbitrary combinations and arbitrary ratios.
Among them, as a solvent contained in the composition for organic electroluminescent elements of the present invention, a solvent having a surface tension at 20 ° C. of usually less than 40 dyn / cm, preferably 36 dyn / cm or less, more preferably 33 dyn / cm or less. Is preferred.

  When a coating film is formed by a wet film-forming method using the composition for organic electroluminescent elements of the present invention, and the polymer of the present invention is crosslinked to form an organic layer, the affinity between the solvent and the base must be high. preferable. This is because the uniformity of film quality greatly affects the uniformity and stability of light emission of the organic electroluminescent device. Accordingly, the composition for an organic electroluminescent element used in the wet film forming method is required to have a low surface tension so that a uniform coating film can be formed with a higher leveling property. Therefore, it is preferable to use a solvent having a low surface tension as described above because a uniform layer containing the polymer of the present invention can be formed, and a uniform crosslinked layer can be formed.

  Specific examples of the low low surface tension solvent include the above-mentioned aromatic solvents such as toluene, xylene, mesitylene, cyclohexylbenzene, ester solvents such as ethyl benzoate, ether solvents such as anisole, trifluoromethoxyanisole, Examples include pentafluoromethoxybenzene, 3- (trifluoromethyl) anisole, and ethyl (pentafluorobenzoate).

On the other hand, as a solvent contained in the composition for organic electroluminescent elements of the present invention, a solvent having a vapor pressure at 25 ° C. of usually 10 mmHg or less, preferably 5 mmHg or less, and usually 0.1 mmHg or more is preferable. . By using such a solvent, a composition for an organic electroluminescent device suitable for the process of producing an organic electroluminescent device by a wet film forming method and suitable for the properties of the polymer of the present invention can be prepared. .
Specific examples of such a solvent include the aforementioned aromatic solvents such as toluene, xylene and mesitylene, ether solvents and ester solvents.

  By the way, the moisture may cause the performance deterioration of the organic electroluminescent device, and in particular, it may promote the decrease in luminance during continuous driving. Therefore, in order to reduce the moisture remaining during wet film formation as much as possible, among the above-mentioned solvents, those having a water solubility of 1% by mass or less at 25 ° C. are preferred, and a solvent having a content of 0.1% by mass or less Is more preferred.

  The content of the solvent contained in the composition for an organic electroluminescent element of the present invention is usually 10% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more, particularly preferably 80% by mass or more . When the content of the solvent is at least the above lower limit, the flatness and the uniformity of the formed layer can be improved.

<Electron Acceptable Compound>
When the composition for an organic electroluminescent element of the present invention is used to form a hole injection layer, it is preferable to further contain an electron accepting compound in order to reduce resistance.
The electron accepting compound is preferably a compound having an oxidizing power and having an ability to accept one electron from the polymer of the present invention. Specifically, a compound having an electron affinity of 4 eV or more is preferable, and a compound having 5 eV or more is more preferable.
Examples of such electron-accepting compounds include triarylboron compounds, metal halides, Lewis acids, organic acids, onium salts, salts of arylamines and metal halides, and salts of arylamines and Lewis acids. One or two or more compounds selected from the group consisting of

  Specifically, onium salts substituted with organic groups such as 4-isopropyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate and triphenylsulfonium tetrafluoroborate (WO 2005/089024); chloride High valence inorganic compounds such as iron (III) (Japanese Unexamined Patent Publication No. 11-251067) and ammonium peroxodisulfate; Cyano compounds such as tetracyanoethylene; Tris (pentafluorophenyl) borane (Japanese Unexamined Patent Publication 2003-2003) No. 31365) and the like; fullerene derivatives, iodine and the like.

The composition for organic electroluminescent elements of the present invention may contain one of the electron accepting compounds as described above alone, or may contain two or more kinds in any combination and ratio.
When the composition for organic electroluminescent elements of the present invention contains an electron-accepting compound, the content of the electron-accepting compound in the composition for organic electroluminescent elements of the present invention is usually 0.0005% by mass or more, preferably 0.8. The content is 001% by mass or more, and usually 20% by mass or less, preferably 10% by mass or less. The ratio of the electron-accepting compound to the polymer of the present invention in the composition for organic electroluminescent elements is usually 0.5% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more. It is 80% by mass or less, preferably 60% by mass or less, and more preferably 40% by mass or less.
The content of the electron-accepting compound in the composition for organic electroluminescent elements is preferably not less than the above lower limit because the electron acceptor accepts electrons from the polymer and the formed organic layer is reduced in resistance. It is preferable that the organic layer formed is less likely to have defects and is less likely to cause film thickness unevenness.

  Moreover, the composition for organic electroluminescent elements of the present invention may further contain a cation radical compound.

As the cation radical compound, an ionic compound composed of a cation radical which is a chemical species obtained by removing one electron from a hole transporting compound and a counter anion is preferable. However, when the cation radical is derived from a hole transporting polymer compound, the cation radical has a structure in which one electron is removed from the repeating unit of the polymer compound.
The cation radical is preferably a chemical species obtained by removing one electron from the compound described above as the hole transporting compound. A chemical species obtained by removing one electron from a compound preferable as a hole transporting compound is preferable in terms of amorphousness, visible light transmittance, heat resistance, solubility, and the like.

  Here, the cation radical compound can be generated by mixing the above-mentioned hole transporting compound and the above-mentioned electron accepting compound. That is, by mixing the above hole transporting compound and the above electron accepting compound, electron transfer occurs from the hole transporting compound to the electron accepting compound, and the cation radical of the hole transporting compound is paired with the cation radical. A cation ion compound consisting of an anion is formed.

  When the composition for organic electroluminescent elements of the present invention contains a cation radical compound, the content of the cation radical compound in the composition for organic electroluminescent elements of the present invention is usually 0.0005% by mass or more, preferably 0.001% by mass. % Or more, and usually 40% by mass or less, preferably 20% by mass or less. When the content of the cation radical compound is not less than the above lower limit, the formed organic layer is preferable because the resistance is reduced, and when it is not more than the above upper limit, the formed organic layer is less likely to have defects and is less likely to cause film thickness unevenness. .

[Organic electroluminescence device]
An organic electroluminescent device according to the present invention comprises an anode and a cathode, and an organic layer between the anode and the cathode on a substrate, wherein the organic layer comprises the polymer according to the present invention. It is preferable that it is a layer formed by the wet film-forming method using the composition for organic electroluminescent elements.
In the organic electroluminescence device of the present invention, the layer formed by the wet film formation method is preferably at least one of a hole injection layer and a hole transport layer. It is preferable that the hole transport layer and the light emitting layer be provided, and the hole injection layer, the hole transport layer and the light emitting layer be all formed by a wet film forming method.

  In the present invention, the wet film forming method is a film forming method, that is, a coating method, for example, spin coating method, dip coating method, die coating method, bar coating method, blade coating method, roll coating method, spray coating method, capillary A method of forming a film by employing a wet film formation method such as a coating method, an ink jet method, a nozzle printing method, a screen printing method, a gravure printing method, or a flexographic printing method, and drying the coated film. Among these film forming methods, a spin coating method, a spray coating method, an inkjet method, a nozzle printing method and the like are preferable.

Hereinafter, an example of the embodiment of the layer configuration of the organic electroluminescent element of the present invention and the general formation method thereof will be described with reference to FIG.
FIG. 1 is a schematic cross-sectional view showing a structural example of an organic electroluminescent element 10 of the present invention. In FIG. 1, 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 Denotes a light emitting layer, 6 denotes a hole blocking layer, 7 denotes an electron transporting layer, 8 denotes an electron injecting layer, and 9 denotes a cathode. As materials applied to these structures, known materials can be applied, and there is no particular limitation, but representative materials and production methods for each layer will be described below as an example. Moreover, when a gazette, a paper, etc. are quoted, the said contents shall be suitably applicable and applicable within the common sense of those skilled in the art.

{substrate}
The substrate 1 is a support of the organic electroluminescent element, and usually, a plate of quartz or glass, a metal plate or metal foil, a plastic film, a sheet or the like is used. Among these, a glass plate and a plate of a transparent synthetic resin such as polyester, polymethacrylate, polycarbonate or polysulfone are preferable. The substrate is preferably made of a material having high gas barrier properties because deterioration of the organic electroluminescent device due to the outside air hardly occurs. For this reason, in particular, when a material having a low gas barrier property such as a synthetic resin substrate is used, it is preferable to provide a dense silicon oxide film or the like on at least one surface of the substrate to improve the gas barrier property.

{anode}
The anode 2 has a function of injecting holes into the layer on the light emitting layer 5 side.
The anode 2 is usually made of a metal such as aluminum, gold, silver, nickel, palladium, or platinum; a metal oxide such as an oxide of indium and / or tin; a metal halide such as copper iodide; a carbon black and a poly (3 -Methylthiophene), polypyrrole, polyaniline and other conductive polymers.

  In general, the anode 2 is often formed by a dry method such as a sputtering method or a vacuum deposition method. In addition, when forming an anode using fine metal particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, and conductive polymer fine powder, an appropriate binder resin solution is used. It can also be formed by dispersing and coating on a substrate. In the case of a conductive polymer, a thin film can be directly formed on a substrate by electrolytic polymerization, or a conductive polymer can be coated on the substrate to form an anode (Appl. Phys. Lett., 60) Volume, 2711 (1992).

The anode 2 usually has a single layer structure, but may have a laminated structure as appropriate. When the anode 2 has a laminated structure, different conductive materials may be laminated on the first anode.
The thickness of the anode 2 may be determined according to required transparency and material. In particular, when high transparency is required, the thickness is preferably such that the visible light transmittance is 60% or more, and more preferably 80% or more. The thickness of the anode 2 is usually 5 nm or more, preferably 10 nm or more, and is usually 1000 nm or less, preferably 500 nm or less. On the other hand, when transparency is not required, the thickness of the anode 2 may be an arbitrary thickness according to the required strength, and in this case, the anode 2 may have the same thickness as the substrate.
In the case of forming another layer on the surface of the anode 2, the impurities on the anode 2 are removed by performing treatment such as ultraviolet light / ozone, oxygen plasma, argon plasma or the like before film formation, and the ionization potential thereof. It is preferable to adjust the hole injection property by adjusting.

{Hole injection layer}
The layer responsible for transporting holes from the anode 2 side to the light emitting layer 5 side is usually called a hole injecting and transporting layer or a hole transporting layer. When there are two or more layers responsible for transporting holes from the anode 2 side to the light emitting layer 5 side, the layer closer to the anode side may be referred to as the hole injection layer 3. The hole injection layer 3 is preferably formed in order to enhance the function of transporting holes from the anode 2 to the light emitting layer 5 side. When forming the hole injection layer 3, the hole injection layer 3 is usually formed on the anode 2.

The thickness of the hole injection layer 3 is usually 1 nm or more, preferably 5 nm or more, and usually 1000 nm or less, preferably 500 nm or less.
The formation method of the hole injection layer may be a vacuum deposition method or a wet film formation method. It is preferable to form by a wet film-forming method at the point which is excellent in the film-forming property.
The hole injection layer 3 preferably contains a hole transporting compound, and more preferably contains a hole transporting compound and an electron accepting compound. Furthermore, it is preferable to include a cation radical compound in the hole injection layer, and it is particularly preferable to include a cation radical compound and a hole transporting compound.
Hereinafter, a general method for forming a hole injection layer will be described. In the organic electroluminescence device of the present invention, the hole injection layer is formed by a wet film formation method using the composition for an organic electroluminescence device of the present invention. Preferably formed by

<Hole transportable compound>
The composition for forming a hole injection layer usually contains a hole transporting compound that becomes the hole injection layer 3. In addition, in the case of a wet film formation method, usually, a solvent is further contained. The composition for forming a hole injection layer preferably has high hole transportability, and can efficiently transport injected holes. For this reason, it is preferable that the hole mobility is large and that an impurity to be a trap is hard to be generated at the time of production or use. Moreover, it is preferable that it is excellent in stability, has a small ionization potential, and has high transparency to visible light. In particular, when the hole injection layer is in contact with the light emitting layer, those that do not quench the light emitted from the light emitting layer or those that form an exciplex with the light emitting layer and do not decrease the light emission efficiency are preferable.

The hole injection layer 3 contains the above-described electron-accepting compound or the above-described cation radical compound because the conductivity of the hole-injection layer can be improved by oxidation of the hole-transporting compound. It is preferable.
Cationic radical compounds derived from high molecular weight compounds such as PEDOT / PSS (Adv. Mater., 2000, 12, 481) and emeraldine hydrochloride (J. Phys. Chem., 1990, 94, 7716) It is also produced by oxidative polymerization (dehydrogenation polymerization).

  The oxidative polymerization referred to herein is to oxidize a monomer chemically or electrochemically in an acidic solution using a peroxodisulfate or the like. In the case of this oxidative polymerization (dehydrogenation polymerization), the monomer is polymerized by oxidation, and the cation radical which is obtained by removing one electron from the repeating unit of the polymer having the anion derived from the acidic solution as a counter anion is Generate

<Formation of hole injection layer by wet film formation method>
When the hole injection layer 3 is formed by a wet film formation method, a material for forming the hole injection layer is usually mixed with a soluble solvent (a solvent for the hole injection layer) to form a film-forming composition (hole An injection layer forming composition), and applying the hole injection layer forming composition onto a layer (usually an anode) corresponding to the lower layer of the hole injection layer, forming a film, and then drying. Form.

  The concentration of the hole transporting compound in the composition for forming a hole injection layer is arbitrary as long as the effects of the present invention are not significantly impaired, but in terms of film thickness uniformity, the lower one is preferable. From the viewpoint that defects are less likely to occur in the hole injection layer, a higher value is preferable. Specifically, the content is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more, and 70% by mass The following is preferable, 60% by mass or less is more preferable, and 50% by mass or less is particularly preferable.

Examples of the solvent include ether solvents, ester solvents, aromatic hydrocarbon solvents, amide solvents, and the like.
Examples of ether solvents include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA), and 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole , Aromatic ethers such as phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole and 2,4-dimethylanisole.

Examples of the ester solvent include aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate.
Examples of the aromatic hydrocarbon solvent include toluene, xylene, cyclohexylbenzene, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropylbenzene, cyclohexylbenzene, methylnaphthalene and the like. It is done. Examples of the amide solvent include N, N-dimethylformamide and N, N-dimethylacetamide.

Besides these, dimethyl sulfoxide and the like can also be used.
Formation of the hole injection layer 3 by a wet film formation method is usually performed after preparing a composition for forming a hole injection layer, and then forming the composition on a layer (usually the anode 2) corresponding to the lower layer of the hole injection layer 3 The film is formed by coating and drying.
In general, the hole injection layer 3 is dried by heating or drying under reduced pressure after film formation. For example, a conventional method disclosed in Japanese Unexamined Patent Application Publication No. 2009-212510 can be applied.

<Formation of hole injection layer by vacuum evaporation method>
When the hole injection layer 3 is formed by vacuum vapor deposition, one or more of the constituent materials of the hole injection layer 3 (the above-described hole transporting compound, electron accepting compound, etc.) are usually vacuumed. Put in a crucible installed in the container (when using two or more kinds of materials, usually put each in separate crucibles), evacuate the vacuum container to about 10 ^-4 Pa with a vacuum pump, then heat the crucible And (if two or more materials are used, usually each crucible is heated) and evaporated while controlling the evaporation amount of the material in the crucible (when two or more materials are used, they are usually independent of each other) The hole injection layer is formed on the anode on the substrate placed facing the crucible. When two or more kinds of materials are used, the hole injection layer can be formed by putting the mixture in a crucible and heating and evaporating the mixture. A conventional method can be applied to the vacuum evaporation method.
The hole injection layer 3 may be cross-linked similarly to the hole transport layer 4 described later.

{Hole transport layer}
The hole transport layer 4 is a layer responsible for transporting holes from the anode 2 side to the light emitting layer 5 side. The hole transport layer 4 is not an essential layer in the organic electroluminescent device of the present invention, but it is preferable to form this layer in order to enhance the function of transporting holes from the anode 2 to the light emitting layer 5 . When forming the hole transport layer 4, the hole transport layer 4 is generally formed between the anode 2 and the light emitting layer 5. When the hole injection layer 3 described above is present, it is formed between the hole injection layer 3 and the light emitting layer 5.

The film thickness of the hole transport layer 4 is usually 5 nm or more, preferably 10 nm or more, and is usually 300 nm or less, preferably 100 nm or less.
The formation method of the hole transport layer 4 may be a vacuum deposition method or a wet film formation method. It is preferable to form by a wet film-forming method at the point which is excellent in the film-forming property.
Hereinafter, a general method for forming a hole transport layer will be described. In the organic electroluminescence device of the present invention, the hole transport layer is formed by a wet film formation method using the composition for organic electroluminescence device of the present invention. Preferably it is formed.

  The hole transport layer 4 usually contains a hole transport compound. As the hole-transporting compound contained in the hole-transporting layer 4, in particular, two or more tertiary compounds represented by 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl Aromatic diamines containing an amine and having two or more fused aromatic rings substituted by nitrogen atoms (Japanese Patent Laid-Open No. 5-234681), 4,4 ′, 4 ′ ′-tris (1-naphthylphenylamino) tri An aromatic amine compound having a starburst structure such as phenylamine (J. Lumin., 72-74, 985, 1997), an aromatic amine compound comprising a tetramer of triphenylamine (Chem. Commun., 2175, 1996), spiro compounds such as 2,2 ′, 7,7′-tetrakis- (diphenylamino) -9,9′-spirobifluorene (Synth. Metals). Vol. 91, 209 pp., 1997), 4,4'-N, carbazole derivatives such as N'- dicarbazole biphenyl. Further, for example, polyvinyl carbazole, polyvinyl triphenylamine (Japanese Unexamined Patent Publication No. 7-53953), polyarylene ether sulfone containing tetraphenylbenzidine (Polym. Adv. Tech., 7, 33, 1996). Etc. can also be used preferably.

<Formation of hole transport layer by wet film formation method>
When forming a hole transport layer by a wet film formation method, in general, in the same manner as in the case of forming the above-described hole injection layer by a wet film formation method, holes are used instead of the hole injection layer forming composition. It forms using the composition for transport layer formation.
When forming a positive hole transport layer by the wet-film-forming method, normally, the composition for positive hole transport layer formation contains a solvent further. As the solvent used for the composition for forming a hole transport layer, the same solvent as the solvent used for the composition for forming a hole injection layer described above can be used.
The concentration of the hole transporting compound in the composition for forming a hole transport layer can be in the same range as the concentration of the hole transporting compound in the composition for forming a hole injection layer.
The formation of the hole transport layer by the wet film formation method can be performed in the same manner as the above-described hole injection layer film formation method.

<Formation of hole transport layer by vacuum evaporation method>
When the hole transport layer is formed by the vacuum deposition method, the hole transport layer is usually used instead of the hole injection layer forming composition in the same manner as in the case of forming the hole injection layer by the vacuum deposition method. It can form using the composition for layer formation. The film formation conditions such as the degree of vacuum at the time of vapor deposition, the vapor deposition rate, and the temperature can be formed under the same conditions as those for the vacuum vapor deposition of the hole injection layer.

{Light emitting layer}
The light emitting layer 5 is a layer having a function of emitting light by being excited by recombination of holes injected from the anode 2 and electrons injected from the cathode 9 when an electric field is applied between a pair of electrodes. . The light emitting layer 5 is a layer formed between the anode 2 and the cathode 9, and the light emitting layer is formed between the hole injection layer and the cathode when there is a hole injection layer on the anode, When there is a hole transport layer on the surface, it is formed between the hole transport layer and the cathode.

The film thickness of the light emitting layer 5 is optional as long as the effects of the present invention are not significantly impaired, but a thicker one is preferable in that defects are not easily generated in the film, and a thinner one is preferable in that a low driving voltage is easily achieved. . For this reason, it is preferably 3 nm or more, more preferably 5 nm or more, and on the other hand, it is usually preferably 200 nm or less, and more preferably 100 nm or less.
The light emitting layer 5 contains at least a material having a property of light emission (light emitting material), and preferably, a material having a charge transporting property (charge transporting material).

<Light emitting material>
The light emitting material emits light at a desired emission wavelength, and is not particularly limited as long as the effects of the present invention are not impaired, and known light emitting materials can be applied. The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, but a material having a good light emitting efficiency is preferable, and a phosphorescent light emitting material is preferable from the viewpoint of the internal quantum efficiency.
As a fluorescent light emitting material, the following materials are mentioned, for example.
As a fluorescent light emitting material (blue fluorescent light emitting material) which gives blue light emission, for example, naphthalene, perylene, pyrene, anthracene, coumarin, chrysene, p-bis (2-phenylethenyl) benzene and derivatives thereof and the like can be mentioned.
Examples of the fluorescent light emitting material that gives green light emission (green fluorescent light emitting material) include quinacridone derivatives, coumarin derivatives, aluminum complexes such as Al (C ₉ H ₆ NO) _3, and the like.

As a fluorescent light emitting material (yellow fluorescent light emitting material) which gives yellow light emission, rubrene, a perimidone derivative, etc. are mentioned, for example.
As a fluorescent light emitting material (red fluorescent light emitting material) giving red light emission, for example, DCM (4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran) based compound, benzopyran derivative, rhodamine derivative Benzothioxanthene derivatives, azabenzothioxanthene and the like.

Examples of the phosphorescent material include organometallic complexes containing a metal selected from Groups 7 to 11 of the long-period periodic table. Preferred examples of the metal selected from Groups 7 to 11 of the periodic table include ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, and gold.
The ligand of the organometallic complex is preferably a ligand in which a (hetero) arylpyridine ligand, a (hetero) aryl group such as a (hetero) arylpyrazole ligand, etc. are linked to pyridine, pyrazole, phenanthroline, etc. In particular, phenylpyridine ligands and phenylpyrazole ligands are preferred. Here, (hetero) aryl represents an aryl group or a heteroaryl group.

  Specific examples of preferred phosphorescent materials include tris (2-phenylpyridine) iridium, tris (2-phenylpyridine) ruthenium, tris (2-phenylpyridine) palladium, bis (2-phenylpyridine) platinum, and tris. Examples include phenylpyridine complexes such as (2-phenylpyridine) osmium and tris (2-phenylpyridine) rhenium, and porphyrin complexes such as octaethyl platinum porphyrin, octaphenyl platinum porphyrin, octaethyl palladium porphyrin, and octaphenyl palladium porphyrin.

  Polymeric light-emitting materials include poly (9,9-dioctylfluorene-2,7-diyl), poly [(9,9-dioctylfluorene-2,7-diyl) -co- (4,4′- (N- (4-sec-butylphenyl)) diphenylamine)], poly [(9,9-dioctylfluorene-2,7-diyl) -co- (1,4-benzo-2 {2,1'-3 } -Triazole)], and polyphenylene vinylene materials such as poly [2-methoxy-5- (2-hexylhexyloxy) -1,4-phenylene vinylene].

<Charge transport material>
The charge transport material is a material having a positive charge (hole) or negative charge (electron) transport property, and is not particularly limited as long as the effect of the present invention is not impaired, and a known light emitting material can be applied.
As the charge transporting material, a compound or the like conventionally used in a light emitting layer of an organic electroluminescence device can be used, and a compound used as a host material of the light emitting layer is particularly preferable.

  Specific examples of charge transporting materials include aromatic amine compounds, phthalocyanine compounds, porphyrin compounds, oligothiophene compounds, polythiophene compounds, benzylphenyl compounds, and compounds in which tertiary amines are linked by a fluorene group. Other than the compounds exemplified as the hole transporting compound of the hole injecting layer such as hydrazone compounds, silazane compounds, silanamine compounds, phosphamine compounds, quinacridone compounds and the like, anthracene compounds, pyrene compounds, Electron transport compounds, such as a carbazole type compound, a pyridine type compound, a phenanthroline type compound, an oxadiazole type compound, a silole type compound, etc. are mentioned.

  In addition, for example, two or more condensed aromatic rings including two or more tertiary amines typified by 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl have nitrogen atoms. Aromatic amine compounds having a starburst structure such as substituted aromatic diamines (Japanese Patent Laid-Open No. 5-234811), 4,4 ′, 4 ″ -tris (1-naphthylphenylamino) triphenylamine ( J. Lumin., 72-74, 985, 1997), an aromatic amine compound comprising a tetramer of triphenylamine (Chem. Commun., 2175, 1996), 2, 2 ′, 7 , 7'-tetrakis- (diphenylamino) -9,9'-spirobifluorene and the like (Synth. Metals, 91, 209, 1997) 4,4'-N, N'compounds exemplified as hole-transporting compound of the positive hole transport layer of the carbazole compounds such as di-biphenyl, or the like can be preferably used. In addition, 2- (4-biphenylyl) -5- (p-tertiarybutylphenyl) -1,3,4-oxadiazole (tBu-PBD), 2,5-bis (1-naphthyl)- Oxadiazole compounds such as 1,3,4-oxadiazole (BND), 2,5-bis (6 ′-(2 ′, 2 ″ -bipyridyl))-1,1-dimethyl-3,4 And silole compounds such as diphenylsilol (PyPySPyPy), phenanthroline compounds such as bathophenanthroline (BPhen) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP, vasocuproin), and the like.

<Formation of light emitting layer by wet film formation method>
The method for forming the light emitting layer may be a vacuum deposition method or a wet film formation method, but a wet film formation method is preferable and a spin coating method and an ink jet method are more preferable because of excellent film forming properties. In particular, when a hole injection layer or a hole transport layer, which is a lower layer of a light emitting layer, is formed using the composition for an organic electroluminescent element of the present invention, it is easy to form a layer by a wet film formation method. It is preferred to adopt the membrane method. When the light emitting layer is formed by a wet film forming method, the light emitting layer is usually used instead of the hole injection layer forming composition in the same manner as in the case of forming the hole injection layer by the wet film forming method. The composition is formed using a composition for forming a light emitting layer prepared by mixing the material as described above with a soluble solvent (solvent for light emitting layer).

  Examples of the solvent include ether solvents, ester solvents, aromatic hydrocarbon solvents, amide solvents, alkane solvents, halogenated aromatic hydrocarbon solvents, fats, and the like mentioned for the formation of the hole injection layer. An aromatic alcohol solvent, an alicyclic alcohol solvent, an aliphatic ketone solvent, an alicyclic ketone solvent, and the like can be given. Although the specific example of a solvent is given to the following, as long as the effect of this invention is not impaired, it is not limited to these. Among these, alkane solvents and aromatic hydrocarbon solvents are particularly preferable.

{Hole blocking layer}
A hole blocking layer 6 may be provided between the light emitting layer 5 and an electron injection layer 8 described later. The hole blocking layer 6 is a layer stacked on the light emitting layer 5 so as to be in contact with the interface of the light emitting layer 5 on the cathode 9 side.
The hole blocking layer 6 has a role to block the transfer of holes transferred from the anode 2 to the cathode 9, and a role to efficiently transport electrons injected from the cathode 9 toward the light emitting layer 5. Have The physical properties required for the material constituting the hole blocking layer 6 include high electron mobility, low hole mobility, a large energy gap (difference between HOMO and LUMO), and excited triplet level (T1). Is high.

  Examples of the material for the hole blocking layer satisfying such conditions include bis (2-methyl-8-quinolinolato) (phenolato) aluminum, bis (2-methyl-8-quinolinolato) (triphenylsilanolato) aluminum, and the like. Mixed metal complexes such as bis (2-methyl-8-quinolato) aluminum-μ-oxo-bis- (2-methyl-8-quinolinato) aluminum binuclear metal complexes, distyrylbiphenyl derivatives, etc. Triazole Derivatives (Styryl Compounds (Japanese Patent Application Laid-Open No. 11-242996), 3- (4-Biphenylyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2,4-triazole, etc. JP-A-7-41759), phenanthroline derivatives such as vasocuproin (JP-A-10-79297) Publication), and the like. Furthermore, a compound having at least one pyridine ring substituted at the 2, 4, 6 position described in WO 2005/022962 is also preferable as a material of the hole blocking layer.

There is no limitation on the method of forming the hole blocking layer 6. Therefore, it can be formed by a wet film formation method, a vapor deposition method, or another method.
The thickness of the hole blocking layer 6 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.3 nm or more, preferably 0.5 nm or more, and usually 100 nm or less, preferably 50 nm or less. is there.

{Electron transport layer}
The electron transport layer 7 is provided between the light emitting layer 5 and the electron injection layer 8 for the purpose of further improving the current efficiency of the device.
The electron transport layer 7 is formed of a compound capable of efficiently transporting electrons injected from the cathode 9 in the direction of the light emitting layer 5 between electrodes to which an electric field is applied. As an electron transporting compound used for the electron transport layer 7, the electron injection efficiency from the cathode 9 or the electron injection layer 8 is high, and it has high electron mobility and can efficiently transport the injected electrons. It is necessary that the compound is capable of

  Specific examples of the electron transporting compound used in the electron transporting layer include, for example, metal complexes such as an aluminum complex of 8-hydroxyquinoline (Japanese Patent Laid-Open No. 59-194393), 10-hydroxybenzo [h]. Metal complexes of quinoline, oxadiazole derivatives, distyrylbiphenyl derivatives, silole derivatives, 3-hydroxyflavone metal complexes, 5-hydroxyflavone metal complexes, benzoxazole metal complexes, benzothiazole metal complexes, trisbenzimidazolylbenzene (US Pat. No. 5645948), quinoxaline compounds (Japanese Unexamined Patent Publication No. 6-207169), phenanthroline derivatives (Japanese Unexamined Patent Publication No. 5-331459), 2-t-butyl-9,10-N, N′-dicyanoanthraquinone. Diimine, n-type hydrogenated amorphous Silicon, n-type zinc sulfide, etc. n-type zinc selenide.

The film thickness of the electron transport layer 7 is usually 1 nm or more, preferably 5 nm or more, and usually 300 nm or less, preferably 100 nm or less.
The electron transport layer 7 is formed by laminating on the hole blocking layer 6 by a wet film formation method or a vacuum deposition method in the same manner as described above. Usually, a vacuum evaporation method is used.

{Electron injection layer}
The electron injection layer 8 plays a role of efficiently injecting electrons injected from the cathode 9 into the electron transport layer 7 or the light emitting layer 5.
In order to perform electron injection efficiently, the material for forming the electron injection layer 8 is preferably a metal having a low work function. Examples include alkali metals such as sodium and cesium, and alkaline earth metals such as barium and calcium. The film thickness is usually preferably 0.1 nm or more and 5 nm or less.
Furthermore, an alkali metal such as sodium, potassium, cesium, lithium or rubidium is doped to an organic electron transport material represented by a metal complex such as a nitrogen-containing heterocyclic compound such as bathophenanthroline or an aluminum complex of 8-hydroxyquinoline ( Japanese Patent Application Laid-Open No. 10-270171, Japanese Patent Application Laid-Open No. 2002-1000047, Japanese Patent Application Laid-Open No. 2002-1000048, and the like, which improve electron injection / transport properties and achieve excellent film quality. It is preferable because it becomes possible.

The film thickness of the electron injection layer 8 is usually 5 nm or more, preferably 10 nm or more, and usually 200 nm or less, preferably 100 nm or less.
The electron injection layer 8 is formed by laminating the light emitting layer 5 or the hole blocking layer 6 or the electron transport layer 7 thereon by a wet film formation method or a vacuum deposition method.
The details of the wet film formation method are the same as those of the light emitting layer described above.

{cathode}
The cathode 9 plays a role of injecting electrons into a layer on the side of the light emitting layer 5 (such as an electron injection layer or a light emitting layer).
As the material of the cathode 9, the material used for the anode 2 can be used. However, in order to perform electron injection efficiently, it is preferable to use a metal having a low work function. And metals such as indium, calcium, aluminum and silver, or alloys thereof. As a specific example, for example, a low work function alloy electrode such as magnesium-silver alloy, magnesium-indium alloy, aluminum-lithium alloy and the like can be mentioned.

From the viewpoint of device stability, it is preferable to protect a cathode made of a metal having a low work function by laminating a metal layer having a high work function and stable to the atmosphere on the cathode. As a metal to laminate | stack, metals, such as aluminum, silver, copper, nickel, chromium, gold, platinum, are mentioned, for example.
The film thickness of the cathode is usually similar to that of the anode.

{Other layers}
The organic electroluminescent device of the present invention may further have other layers as long as the effects of the present invention are not significantly impaired. That is, any other layer described above may be provided between the anode and the cathode.

{Other element configurations}
The organic electroluminescent device of the present invention has a structure opposite to that described above, that is, a cathode, an electron injection layer, an electron transport layer, a hole blocking layer, a light emitting layer, a hole transport layer, and a hole injection layer on the substrate. It is also possible to laminate in order of, and an anode.
When the organic electroluminescent element of the present invention is applied to an organic electroluminescent device, it may be used as a single organic electroluminescent element, or may be used in a configuration in which a plurality of organic electroluminescent elements are arranged in an array, The anode and the cathode may be used in a configuration in which they are arranged in an XY matrix.

[Organic EL display device]
The organic electroluminescent device display device (organic EL display device) of the present invention uses the above-described organic electroluminescent device of the present invention. There is no restriction | limiting in particular about the model and structure of the organic electroluminescent display apparatus of this invention, It can assemble in accordance with a conventional method using the organic electroluminescent element of this invention.
For example, the organic EL display device of the present invention can be obtained by the method described in “Organic EL display” (Ohm, published on Aug. 20, 2004, Shizushi Tokito, Chiba Adachi, Hideyuki Murata). Can be formed.

[Organic EL lighting]
The organic electroluminescent device illumination (organic EL illumination) of the present invention uses the above-described organic electroluminescent device of the present invention. There are no particular restrictions on the type and structure of the organic EL lighting of the present invention, and the organic electroluminescent device of the present invention can be assembled according to a conventional method.

(Synthesis of model compound)

In a stream of nitrogen, 3- (1-pyrenyl) phenylboronic acid, 2.11 g (6.56 mmol), 4-bromocyclobutene, 1.20 g (6.56 mmol), toluene: ethanol (30 ml: 15 ml), 2 M carbonate 15 ml of aqueous sodium solution was stirred for 40 minutes while heating to 60 ° C., tetrakis (triphenylphosphine) palladium (0), 0.15 g (0.13 mmol) was added, and the mixture was refluxed for 6 hours. After cooling to room temperature, toluene (100 ml) and water (120 ml) are added to the reaction solution and stirred, and then separated, the aqueous layer is extracted with toluene (100 ml × 2 times), the organic layers are combined, and magnesium sulfate is used. After drying, it was concentrated. Further, the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 9: 1) to obtain Compound 1 (1.80 g).
¹ H-NMR (400 MHz, CDCl ₃ ) δ 3.23 (s, 4 H); 7.13 (d, 1 H); 7.38 (s, 1 H); 7.5 1 to 7. 68 (m, 4 H) 7.82 to 8.04 (m, 4H); 8.10 (s, 2H); 8.15 to 8.25 (m, 4H).

It is dissolved in 15 ml of 1,2-dihydrocyclobuta [a] naphthalene, 1.00 g (6.48 mmol), N, N-dimethylformamide, N-bromosuccinimide, 1.15 g (6.48 mmol) in 10 ml of N , Dissolved in N-dimethylformamide and added dropwise at room temperature. The reaction was allowed to proceed at room temperature for 98 hours. Pure water was added to the reaction solution, and liquid separation was performed with methylene chloride. The organic layer was concentrated and purified by silica gel column chromatography (acetonitrile: tetrahydrofuran = 9: 1) to give compound 2 (0.56 g).
¹ H-NMR (400 MHz, CDCl ₃ ) δ 3.28 to 3.35 (m, 4 H); 7.49 to 7.53 (m, 2 H); 7.56 (s, 1 H); 7.70 (m, 1H); 8.26-8.30 (m, 1H).

In a nitrogen stream, 3- (1-pyrenyl) phenylboronic acid, 2.38 g (7.39 mmol), compound 2, 2.07 g (8.88 mmol), toluene: ethanol (60 ml: 30 ml), 2 M aqueous sodium carbonate solution 22 ml The mixture was stirred at 60 ° C. for 40 minutes, tetrakis (triphenylphosphine) palladium (0), 0.26 g (0.22 mmol) was added, and the mixture was refluxed for 3 hours. After cooling to room temperature, toluene (200 ml) and water (240 ml) were added to the reaction solution and stirred, and then separated, the aqueous layer was extracted with toluene (100 ml × 2 times), the organic layers were combined, and magnesium sulfate was used. After drying, it was concentrated. Further, the residue was purified by silica gel column chromatography (hexane: methylene chloride = 6: 1) to obtain Compound 3 (3.20 g).
¹ H-NMR (400 MHz, CDCl ₃ ) δ 3.33 to 3.45 (m, 4 H); 7.31 (s, 1 H); 7.39 to 7.48 (m, 2 H); 7.77 (m, 5H); 7.95 to 8.30 (m, 10H).

(Reference example)
When differential scanning calorimetry (DSC) of Compound 1 was performed using DSC-50 manufactured by Shimadzu Corporation, an exotherm associated with the crosslinking reaction was observed, and the peak top was at 262 ° C. Similarly, when differential scanning calorimetry of Compound 3 was performed, an exotherm associated with the crosslinking reaction was observed, and the peak top was 235 ° C., which was 27 ° C. lower than the measurement result of Compound 1.

  From these results, it was confirmed that 1,2-dihydrocyclobuta [a] naphthalene contained in the compound 3 undergoes a crosslinking reaction at a temperature 27 ° C. lower than that of the benzocyclobutene contained in the compound 1. Therefore, the polymer having 1,2-dihydrocyclobuta [a] naphthalene as a crosslinking group according to the present invention is insoluble in a solvent at a lower temperature than the conventional polymer having benzocyclobutene as a crosslinking group. It is considered to be.

(Synthesis of monomer)

  Under a nitrogen stream, 100 ml of dimethyl sulfoxide, Compound 2, 4.8 g (20.6 mmol), bis (pinacolato) diboron 5.75 g (22.7 mmol), potassium acetate 6.1 g (61.8 mmol) were added at 60 ° C. For 30 minutes. 0.51 g (0.62 mmol) of 1,1'-bis (diphenylphosphino) ferrocene palladium (II) dichloride dichloromethane was added and stirred at 82 ° C for 4 hours. The reaction solution was filtered under reduced pressure, the filtrate was extracted with toluene, dried over anhydrous magnesium sulfate, and roughly purified with activated clay. The product was further washed with acetonitrile to give Compound 4 as a colorless solid (yield 4.0 g, 69.3%).

  Under a nitrogen stream, 0.78 g (4.54 mmol) of 3-bromoaniline, 1.40 g (5.00 mmol) of compound 4, sodium carbonate (2.41 g, 22.7 mmol), 30 ml of toluene, 15 ml of ethanol, and 12 ml of water Was warmed to 65 ° C. Tetrakis (triphenylphosphine) palladium (0.26 g, 0.23 mmol) was added and heated to reflux under nitrogen for 6 hours. After allowing to cool, the mixture was extracted with ethyl acetate, and the organic layer was dried over magnesium sulfate and concentrated. Further, the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 8: 1) to give compound 5 (0.59 g).

  Under a nitrogen stream, 1,3,5-tribromobenzene, 3.00 g (9.53 mmol), compound 4, 1.34 g (4.77 mmol), sodium carbonate (2.53 g, 23.85 mmol), and toluene 80 ml 40 ml of ethanol and 12 ml of water were warmed to 65.degree. Tetrakis (triphenylphosphine) palladium (0.11 g, 0.095 mmol) was added and heated to reflux under nitrogen for 4.5 hours. After allowing to cool, the mixture was extracted with toluene, and the organic layer was dried over magnesium sulfate and concentrated. Further, the residue was purified by silica gel column chromatography (hexane) to obtain Compound 6 (1.00 g).

  Under a nitrogen stream, 4.67 g (12.65 mmol) of 4,4 ′-[1- (4-bromophenyl) ethylidene] bisphenol, 3.90 g (13.92 mmol) of compound 4, and 80 ml of 1,2-dimethoxyethane were added. Stir at room temperature. To this was added 22 ml of 2M aqueous potassium carbonate solution. 0.29 g (0.25 mmol) of tetrakis (triphenylphosphine) palladium was added, and the mixture was heated to reflux for 4 hours. After allowing to cool, the mixture was extracted with ethyl acetate, and the organic layer was dried over magnesium sulfate and concentrated. Furthermore, the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 3: 1) to give compound 7 (5.50 g).

  At −5 ° C., compound 7, 5.50 g (12.43 mmol) was dissolved in methylene chloride (90 ml) and triethylamine 6.30 g (62.15 mmol), and trifluoromethanesulfonic anhydride 10.5 g (37.3 mmol) was dissolved. A solution of 1 in 17 ml of methylene chloride was added dropwise. Stir for 4 hours and pour the reaction solution into ice water. The mixture was extracted with methylene chloride, and the organic layer was dried over magnesium sulfate and concentrated. Purification by silica gel column chromatography (hexane: methylene chloride = 3: 1) gave compound 8 (7.3 g).

  Under a nitrogen stream, Compound 8, 7.1 g (10.05 mmol), bis (pinacolato) diboron 6.1 g (24.11 mmol), potassium acetate 5.90 g (60.3 mmol) dimethyl sulfoxide 100 ml was stirred at 60 ° C. for 30 minutes. did. 0.41 g (0.50 mmol) of 1,1′-bis (diphenylphosphino) ferrocene palladium (II) dichloride dichloromethane was added, and the mixture was stirred at 85 ° C. for 3.5 hours. The reaction solution was filtered under reduced pressure, the filtrate was extracted with toluene, the organic layer was dried over anhydrous magnesium sulfate, the filtrate was concentrated, methanol was added, and the precipitated colorless solid was collected by filtration to give compound 9 (3.6 g). I got

  Under a nitrogen stream, compound 9, 3.6 g (5.43 mmol), 1-bromo-4-iodobenzene 3.38 g (11.96 mmol), toluene 120 ml, ethanol 60 ml, and 2M aqueous potassium phosphate solution 18 ml were added and heated. And stirred for 30 minutes. 0.28 g (0.24 mmol) of tetrakis (triphenylphosphine) palladium was added and refluxed for 4.5 hours. Water was added to the reaction solution, extraction was performed with toluene, anhydrous magnesium sulfate and activated clay were added to the organic layer, and the filtrate was concentrated. Purification by adsorption silica gel column chromatography (developing solvent: n-hexane: toluene = 4: 1) gave compound 10 (2.1 g) as a colorless solid.

(Synthesis of polymer)

  2,7-bis (4-bromophenyl) -9,9-dihexylfluorene (3.500 g, 5.43 mmol), 2-amino-9,9-dihexylfluorene (3.80 g, 10.87 mmol), and tert Sodium butoxy (4.02 g, 41.9 mmol) and toluene (80.7 ml) were charged, and the inside of the system was replaced with nitrogen and heated to 60 ° C. (solution A). To a 6.5 ml toluene solution of tris (dibenzylideneacetone) dipalladium complex (0.100 g, 0.109 mmol), [4- (N, N-dimethylamino) phenyl] di-tert-butylphosphine (0.231 g, 0.868 mmol) was added and warmed to 60 ° C. (solution B). In a nitrogen stream, solution B was added to solution A and heated to reflux for 1 hour. 2,7-Bis (4-bromophenyl) -9,9-dihexylfluorene (2.450 g, 3.80 mmol) was added and heated to reflux for 1 hour. Furthermore, compound 10 (0.783 g, 1.087 mmol) was added, and after heating back for 1 hour, bromobenzene (0.85 g, 5.43 mmol) was added, and heating reflux reaction was performed for 1.5 hours. The reaction solution was allowed to cool, 100 ml of toluene was added, and the solution was added dropwise to a solution of ethanol / water (500 ml / 90 ml) to obtain a crude polymer.

The crude polymer was dissolved in toluene and reprecipitated in acetone, and the precipitated polymer was collected by filtration. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated into ammonia-containing ethanol. The polymer collected by filtration was purified by column chromatography to obtain polymer 1 (4.3 g).
Weight average molecular weight (Mw) = 44100
Number average molecular weight (Mn) = 30,200
Degree of dispersion (Mw / Mn) = 1.46

  4,4′-Dibromobiphenyl (2.678 g, 8.58 mmol), 2-amino-9,9-dihexylfluorene (6.00 g, 17.17 mmol), and sodium tert-butoxy (5.53 g, 57.50 mmol) ), Toluene (90 ml) was charged, and the system was replaced with nitrogen and heated to 60 ° C. (solution A). To a solution of tris (dibenzylideneacetone) dipalladium complex (0.158 g, 0.172 mmol) in 12 ml toluene was added [4- (N, N-dimethylamino) phenyl] di-tert-butylphosphine (0.365 g, 376 mmol) were added and warmed to 60 ° C. (solution B). In a nitrogen stream, solution B was added to solution A, and heated to reflux for 1.0 hour. Compound 6 (0.333 g, 0.858 mmol) was heated under reflux for 30 minutes, and then 4,4'-dibromobiphenyl (2.276 g, 7.294 mmol) was added. After heating at reflux for 1.0 hour, bromobenzene (2.02 g, 12.87 mmol) was added. The reaction was heated to reflux for 1.5 hours. The reaction solution was allowed to cool, 100 ml of toluene was added, and the solution was added dropwise to a solution of ethanol / water (500 ml / 90 ml) to obtain a crude polymer.

The crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was collected by filtration. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated into ammonia-containing ethanol. The polymer collected by filtration was purified by column chromatography to obtain polymer 2 (0.7 g).
Weight average molecular weight (Mw) = 50300
Number average molecular weight (Mn) = 36400
Degree of dispersion (Mw / Mn) = 1.38

  4,4'-Dibromobiphenyl (2.500 g, 8.00 mmol), 2-amino-9,9-dihexylfluorene (5.60 g, 16.00 mmol), and tert-butoxy sodium (5.93 g, 61.8 mmol) ) And toluene (57.7 ml) were charged, and the system was replaced with nitrogen and heated to 60 ° C. (solution A). [4- (N, N-dimethylamino) phenyl] di-tert-butylphosphine (0.340 g) in a solution of 9.5 ml of tris (dibenzylideneacetone) dipalladium complex (0.147 g, 0.160 mmol) in toluene 1.282 mmol) was added and warmed to 60 ° C. (solution B). In a nitrogen stream, solution B was added to solution A and heated to reflux for 1 hour. 4,4'-Dibromobiphenyl (2.015 g, 6.46 mmol) was added and heated to reflux for 1 hour. Furthermore, compound 10 (0.716 g, 0.994 mmol) was added, and after heating back for 1 hour, bromobenzene (1.26 g, 8.02 mmol) was added, and heating reflux reaction was performed for 1.5 hours. The reaction solution was allowed to cool, 100 ml of toluene was added, and the solution was added dropwise to a solution of ethanol / water (500 ml / 90 ml) to obtain a crude polymer.

The crude polymer was dissolved in toluene and reprecipitated in acetone, and the precipitated polymer was collected by filtration. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated into ammonia-containing ethanol. The polymer collected by filtration was purified by column chromatography to obtain polymer 3 (1.1 g).
Weight average molecular weight (Mw) = 37100
Number average molecular weight (Mn) = 27700
Degree of dispersion (Mw / Mn) = 1.34

  4,4′-dibromobiphenyl (3.83 g, 12.22 mmol), compound 5 (0.299 g, 1.22 mmol), 2-amino-9,9-dihexylfluorene (8.10 g, 23.18 mmol), and Sodium tert-butoxy (7.86 g, 81.74 mmol) and 120 ml of toluene were charged, and the system was replaced with nitrogen and heated to 60 ° C. (solution A). To a solution of tris (dibenzylideneacetone) dipalladium complex (0.22 g, 0.244 mmol) in 15 ml of toluene, [4- (N, N-dimethylamino) phenyl] di-tert-butylphosphine (0.518 g, 1. 95 mmol) were added and warmed to 60 ° C. (solution B). In a nitrogen stream, solution B was added to solution A, and heated to reflux for 1.0 hour. 1,4-Dibromobiphenyl (2.66 g, 8.54 mmol) was added. After heating to reflux for 1.0 hour, 4,4'-dibromobiphenyl (0.88 g, 2.83 mmol) was additionally added. After heating to reflux for 1.0 hour, bromobenzene (2.88 g, 18.34 mmol) was added. The reaction was heated to reflux for 1.5 hours. The reaction solution was allowed to cool, 150 ml of toluene was added, and added dropwise to a solution of ethanol / water (500 ml / 90 ml) to obtain a crude polymer.

The crude polymer was dissolved in toluene and reprecipitated in acetone, and the precipitated polymer was collected by filtration. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated into ammonia-containing ethanol. The polymer collected by filtration was purified by column chromatography to obtain polymer 4 (4.1 g).
Weight average molecular weight (Mw) = 46700
Number average molecular weight (Mn) = 33,800
Degree of dispersion (Mw / Mn) = 1.38

[Measurement of insolubilization rate]
Example 1
The film thicknesses L1 and L2 were measured by the following method, and L2 / L1 was defined as the insolubilization rate.

<Deposition method and measurement method of film thickness L1>
A 4 mass% cyclohexylbenzene solution (composition) of polymer 1 (Mw = 44100, Mn = 30200, Mw / Mn = 1.46) was prepared, and the composition was spin-coated on a glass substrate to form a film. .

  Spin coating was performed in nitrogen at a spinner rotation speed of 2400 rpm and a spinner rotation time of 120 seconds. After spin coating, it was dried for 10 minutes at 210 ° C. on a hot plate in nitrogen. A part of the obtained film was scraped off, and the film thickness L1 (nm) was measured with a step meter (Tencor P-15).

<Method of measuring film thickness L2>
The substrate after the film thickness L1 measurement was set in a spinner, dropped to the position where the film thickness was measured of cyclohexylbenzene, and after standing for 30 seconds, it was spun out. In order to evaporate cyclohexylbenzene, after baking on a hot plate, the film thickness L2 (nm) at the same place was measured again, and the insolubilization ratio L2 / L1 after spin treatment of cyclohexylbenzene was calculated.

  L1 = 58.0 nm, L2 = 49.9 nm, and the insolubilization rate of the polymer 1 was 86%.

(Example 2)
In the same manner as in Example 1, the insolubilization rate of the polymer 2 (Mw = 50300, Mn = 36400, Mw / Mn = 1.38) was measured.

  L1 = 51.2 nm, L2 = 41.5 nm, and the insolubilization rate of the polymer 2 was 81%.

(Example 3)
In the same manner as in Example 1, the insolubilization rate of the polymer 3 (Mw = 37100, Mn = 27700, Mw / Mn = 1.34) was measured.

  L1 = 50.7 nm and L2 = 46.6 nm, and the insolubilization rate of the polymer 3 was 92%.

(Example 4)
In the same manner as in Example 1, the insolubilization rate of the polymer 4 (Mw = 46700, Mn = 33800, Mw / Mn = 1.38) was measured.

  L1 = 52.2 nm, L2 = 48.6 nm, and the insolubilization rate of the polymer 4 was 93%.

(Comparative example 1)
In the same manner as in Example 1, the insolubilization rate of the polymer 5 (Mw = 50000, Mn = 33300, Mw / Mn = 1.50) was measured.

  L1 = 78.8 nm, L2 = 0 nm, and the insolubilization ratio of the polymer 5 was 0%.

(Comparative example 2)
In the same manner as in Example 1, the insolubilization rate of polymer 6 (Mw = 38900, Mn = 27600, Mw / Mn = 1.41) was measured.

  L1 = 50.4 nm, L2 = 0 nm, and the insolubilization rate of the polymer 6 was 0%.

(Comparative example 3)
In the same manner as in Example 1, the insolubilization rate of the polymer 7 (Mw = 48000, Mn = 33100, Mw / Mn = 1.45) was measured.

  L1 = 52.6 nm, L2 = 0 nm, and the insolubilization rate of the polymer 7 was 0%.

  The measurement results of the insolubilization rates of Examples 1 to 4 and Comparative Examples 1 to 3 are summarized in Table 1.

  As shown in Table 1, the polymer of the present application having 1,2-cyclobuta [a] naphthalene as a crosslinkable group was insolubilized. On the other hand, the conventional polymer having benzocyclobutene which is a crosslinkable group was not insolubilized.

[Organic electroluminescence device]
(Example 5)
An organic electroluminescent device shown in FIG. 1 was produced.
An indium tin oxide (ITO) transparent conductive film deposited by sputtering on a glass substrate 1 is patterned into stripes of 2 mm in width using ordinary photolithography technology and hydrochloric acid etching to a film thickness of 70 nm Anode 2 was formed. The patterned ITO substrate is cleaned in the order of ultrasonic cleaning with an aqueous surfactant solution, water cleaning with ultrapure water, ultrasonic cleaning with ultrapure water, and water cleaning with ultrapure water, followed by drying with compressed air, and finally UV irradiation. Ozone cleaning was performed.
Next, a coating solution for forming a hole injection layer containing the polymer 7, 4-isopropyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate shown in the structural formula (A1) and ethyl benzoate is prepared. did. This coating liquid was formed into a film by spin coating on the anode 2 and heated under the following conditions to obtain a hole injecting layer having a film thickness of 40 nm.

Coating solution for forming hole injection layer
Solvent Ethyl benzoate Coating solution concentration Polymer 7: 2.5% by mass
A1: 0.5% by mass
<Deposition condition of hole injection layer 3>
Spin coat atmosphere Atmospheric heating condition Atmospheric 240 ° C 10 minutes

  Subsequently, a coating solution for forming a hole transport layer containing the following polymer 1 was prepared, and a hole transport layer having a thickness of 40 nm was formed by spin coating on the hole injection layer 3 under the following conditions and heating. It formed.

<Coating liquid for hole transport layer formation>
Solvent: Cyclohexylbenzene Coating solution concentration: 1.5% by mass
<Deposition condition of hole transport layer 4>
Spin coating atmosphere In nitrogen Heating conditions In nitrogen 220 ° C 10 minutes

  Next, a light emitting layer forming coating solution containing the compounds (H1), (H2), and (D1) shown in the following structural formula is prepared, and film formation is performed by spin coating under the following conditions, followed by heating. Thus, a light emitting layer having a thickness of 50 nm was formed on the hole transport layer 4.

<Light emitting layer forming coating solution>
Solvent Cyclohexylbenzene Coating solution concentration H1: 1.2% by mass
H2: 3.6% by mass
D1: 0.48 mass%
<Film formation conditions of the light emitting layer 5>
Spin coating atmosphere In nitrogen Heating conditions In nitrogen 130 ° C 10 minutes

  Here, the substrate on which the light emitting layer has been formed is transferred into a vacuum vapor deposition apparatus, and an organic compound (E1) having the structure shown below is laminated on the light emitting layer 5 by a vacuum vapor deposition method to obtain a film thickness of 15 nm. The hole blocking layer 6 was formed.

  Next, an organic compound (E2) having a structure shown below was laminated on the hole blocking layer 6 by a vacuum evaporation method to form an electron transport layer 7 with a thickness of 20 nm.

  Here, the element on which the electron transport layer 7 has been deposited is transferred to another vacuum deposition apparatus, and a 2 mm wide striped shadow mask is used as a cathode deposition mask so that it is orthogonal to the ITO stripe of the anode 2. It was made to adhere to. As the electron injection layer 8, first, lithium fluoride (LiF) was formed on the electron transport layer 7 with a film thickness of 0.5 nm by a vacuum evaporation method using a molybdenum boat. Next, aluminum was similarly heated as a cathode 9 by a molybdenum boat, and an aluminum layer with a film thickness of 80 nm was formed by a vacuum evaporation method. The substrate temperature at the time of vapor deposition of the above two layers was kept at room temperature.

Subsequently, in order to prevent the element from being deteriorated due to moisture and the like in the air during storage, sealing treatment was performed by the method described below.
In a nitrogen glove box, a photocurable resin (30Y-437 manufactured by Three Bond Fine Chemical Co., Ltd.) is applied with a width of about 1 mm on the outer peripheral part of a 23 mm × 23 mm size glass plate, and a moisture getter sheet (Dinic Co., Ltd.) Company). On this, the substrate on which the formation of the cathode was completed was pasted so that the vapor-deposited surface faced the desiccant sheet. After that, ultraviolet light was irradiated only to the area where the photocurable resin was applied to cure the resin.

  As described above, an organic electroluminescent device having a light emitting area with a size of 2 mm × 2 mm was obtained. The characteristics of this element are shown in Table 2.

(Comparative example 4)
The organic electroluminescent element was prepared in the same manner as in Example 5 except that the hole transport layer 4 was prepared by preparing a coating liquid for forming a hole transport layer containing the polymer 5 and forming the film by spin coating and heating. Created. The characteristics of this element are shown in Table 2.

<Coating liquid for forming hole transport layer>
Solvent: Cyclohexylbenzene Coating solution concentration: 1.5% by mass
<Deposition condition of hole transport layer 4>
Spin coating atmosphere In nitrogen Heating conditions In nitrogen 220 ° C 10 minutes

  As is clear from Table 2, it was found that the organic electroluminescent device using the polymer of the present invention had a low voltage.

(Example 6)
A coating solution for forming a hole injection layer containing polymer 2, 4-isopropyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate and ethyl benzoate represented by the formula (A1) under the following conditions: Prepared. An organic electroluminescent element was produced in the same manner as in Example 5 except that this coating solution was formed on the anode 2 by spin coating and heated under the following conditions to form a 40-nm-thick hole injection layer. . The characteristics of this element are shown in Table 3.

Coating solution for forming hole injection layer
Solvent Ethyl benzoate Coating solution concentration Polymer 2: 2.5% by mass
A1: 0.5% by mass
<Deposition condition of hole injection layer 3>
Spin coat atmosphere Atmospheric heating condition Atmospheric 220 ° C 10 minutes

(Example 7)
An organic electroluminescent element was produced in the same manner as in Example 6 except that the polymer used for the hole injection layer forming coating solution was changed from the polymer 2 to the polymer 3. Table 3 shows the characteristics of this element.

(Example 8)
The organic electroluminescent element was produced like Example 6 except having replaced the polymer used for the coating liquid for positive hole injection layer formation from the polymer 2 to the polymer 4. The characteristics of this element are shown in Table 3.

(Comparative example 5)
The polymer used for the hole injection layer forming coating solution is changed from the polymer 2 to the polymer 7, and the polymer used for the hole transport layer forming coating solution is changed from the polymer 1 to the polymer 5. In the same manner as in Example 6, an organic electroluminescent device was produced. The characteristics of this element are shown in Table 3.

  As is clear from Table 3, it was found that the organic electroluminescent device using the polymer of the present invention had a low voltage.

  Although the invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application (Japanese Patent Application No. 2014-040769) filed on March 3, 2014, the contents of which are incorporated herein by reference.

  Since the polymer of the present invention is excellent in electrochemical stability, an element including a layer formed using the polymer may be a flat panel display (for example, for OA computers or wall-mounted televisions), an on-vehicle display element, a mobile phone. It can be applied to light sources (for example, light sources for copiers, backlights for liquid crystal displays and instruments), display panels, and beacon lamps that take advantage of the characteristics of telephone displays and surface light emitters, and their technical value is great. It is a thing.

Claims (12)

Have a crosslinking group represented by the following formula (1), as a partial structure, triarylamine structure, three or more rings of the aromatic ring structure, charge transport to have a heteroaromatic ring structure or a metal complex structure, Polymer.

(The 1,2-dihydrocyclobuta [a] naphthalene ring in formula (1) may have a substituent.) The charge transporting polymer according to claim 1, which contains a repeating unit represented by the following formula (2).

(In the formula (2), p represents an integer of 0 or more and 3 or less,
Ar ¹ and Ar ² each independently represent a direct bond, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent,
Ar ^{3 to} Ar ⁵ each independently represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent,
However, neither Ar ¹ nor Ar ² is a direct bond. ) The charge transporting polymer according to claim 1, which contains a repeating unit represented by the following formula (3).

(In the formula (3), q represents an integer of 0 or more and 3 or less,
R ¹ is an optionally substituted alkyl group having 1 to 24 carbon atoms, an optionally substituted aromatic hydrocarbon group, or an optionally substituted aromatic heterocyclic ring. Represents a group,
Ar ⁶ and Ar ⁷ each independently represent a direct bond, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent,
Ar ^{8 to} Ar ¹² each independently represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent,
However, neither Ar ⁶ nor Ar ⁷ is a direct bond. ) The charge transporting polymer according to claim 1, which contains a repeating unit represented by the following formula (4).

(In the formula (4), r represents an integer of 0 or more and 3 or less,
Ar ¹³ , Ar ¹⁴ , Ar ¹⁶ and Ar ¹⁷ each independently represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent,
Ar ¹⁵ represents a direct bond, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. ) The charge transporting polymer according to any one of claims 1 to 4, wherein the weight average molecular weight (Mw) is 20,000 or more and the dispersity (Mw / Mn) is 2.5 or less. The composition for organic electroluminescent elements containing the charge transportable polymer as described in any one of Claims 1-5. An organic electroluminescent device comprising an anode, a cathode, and an organic layer between the anode and the cathode on a substrate,
The organic electroluminescent element in which this organic layer contains the layer formed with the wet film-forming method using the composition for organic electroluminescent elements of Claim 6.   The organic electroluminescent device according to claim 7, wherein the layer formed by the wet film formation method is at least one of a hole injection layer and a hole transport layer.   A positive hole injection layer, a positive hole transport layer and a light emitting layer are included between the anode and the negative electrode, and the positive hole injection layer, the positive hole transport layer and the light emitting layer are all formed by a wet film formation method. The organic electroluminescent element of Claim 7 or Claim 8.   The organic electroluminescence display which has an organic electroluminescent element as described in any one of Claims 7-9.   Organic EL illumination which has the organic electroluminescent element as described in any one of Claims 7-9. The compound represented by following formula (5).

(In formula (5), X represents a halogen atom.)

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